The invention relates to novel materials based on modified oxidic materials, such as, for example, tin oxides, as active positive-electrode material in electrochemical cells.
Lithium ion batteries are amongst the most promising systems for mobile applications. The areas of application extend from high-quality electronic equipment (for example mobile telephones, camcorders) to batteries for electrically driven motor vehicles.
These batteries may include a negative electrode, a positive electrode, a separator and a non-aqueous electrolyte. The negative electrode is typically Li(MnMez)2O4, Li(CoMez)O2, Li(CoNixMez)O2 or other lithium intercalation and insertion compounds. Positive electrodes can consist of lithium metal, soft and hard carbons, graphite, graphitic carbons or other lithium intercalation and insertion compounds or alloy compounds. As electrolyte, use is made of solutions containing lithium salts, such as LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiN(CF3SO2)2 or LiC(CF3SO2)3 and mixtures thereof in aprotic solvents.
In the lithium ion batteries currently commercially available, carbon is employed as positive electrode. However, this positive-electrode system has some problems. A considerable drop in capacity occurs in this system during the 1st cycle due to irreversible incorporation of lithium into the carbon structure. In addition, the cycle stability of the carbons and graphites available is unsatisfactory. Furthermore, there is the safety aspect that kinetic limitations can cause critical parameters.
In order to improve the positive-electrode properties, new systems are being sought to replace, for example, the carbon positive electrode. A variety of efforts are being made here. The carbon materials are being replaced, for example, by oxidic materials or alloys. In Journal of Power Sources 75 (1998), Wolfenstine investigates the suitability of tin oxide/tin mixtures as positive-electrode material for lithium ion batteries. The irreversible loss of Li due to the formation of Li2O is said to be minimized by the preferred use of SnO over SnO2. EP 0823742 describes tin mixed oxides doped with various metals. U.S. Pat. No. 5,654,114 also describes the use of tin oxides as positive-electrode material for secondary lithium ion batteries. All the systems investigated have the drawback that Li is converted into Li2O. This means that a large amount of Li is bound, and therefore is not available for the electrochemical processes in the battery.
One feature of the present invention is to provide positive-electrode materials which offer better charging/discharging behaviour compared with carbon. The better behaviour should be characterized by higher capacities and good cycle stability.
This feature according to the invention can be achieved by the use of modified tin oxides, which are used as positive-electrode material in electrochemical cells.
It has been found that reduction of the tin oxide by means of reducing gases results in an improved positive-electrode system. This system consists of a mixture of tin oxide and tin particles which is finely distributed in the tin oxide grains and the conventional additives (for example PTFE, or PVDF; solvents, e.g. nonpolar solvents; and conductive black). Conductive black is provided in amounts of, generally, about 1-about 5% by weight; preferably about 3% by weight; PTFE or PVDF is provided in amounts of, generally, about 20-about 40% by weight, preferably about 35% by weight; and at least one solvent is provided in amounts of, generally, about 5-about 20% by weight, preferably about 12% by weight.
Surprisingly, it has been found that the modified tin oxide systems have excellent electrochemical properties. The irreversible loss of lithium during the 1st cycle is still observed. However, it is not as pronounced as before the treatment of the tin oxide SnO2.
The prior-art uses of tin oxides for positive-electrode materials have the problem of particle agglomeration. Surprisingly, it has been found that the process according to the invention enables the production of particles of defined diameter. The process according to the invention enables the production of primary particles in the nm range and secondary particles having a diameter of less than 10 xcexcm. These small particles result in an increase in the active surface area.
The process for the preparation of the positive-electrode material is characterized in that
a) urea is added to a tin chloride solution,
b) urotropin is added to the solution,
c) the resultant sol is emulsified in petroleum ether,
d) the resultant gel is washed, and the solvent is removed by suction,
e) the gel is dried and heat-treated, and
f) the resultant SnO2 is exposed to a reducing gas stream in an aeratable furnace.
The materials according to the invention are suitable for use in electrochemical cells, preferably in batteries, particularly preferably in secondary lithium ion batteries.
The positive-electrode material according to the invention can be employed in secondary lithium ion batteries with customary electrolytes. Examples of suitable electrolytes are those comprising conductive salts selected from the group consisting of LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiN(CF3SO2)2 and LiC(CF3SO2)3, and mixtures thereof. The electrolytes may also comprise organic isocyanates (DE 199 44 603) for reducing the water content. The electrolytes may also comprise organic alkali metal salts (DE 199 10 968) as additive. Suitable are alkali metal borates of the general formula
Li+Bxe2x88x92(OR1)m(OR2)p
in which
m and p are 0, 1, 2, 3 or 4, where m+p=4, and
R1 and R2 are identical or different,
are optionally bonded directly to one another via a single or double bond,
are each, individually or together, an aromatic or aliphatic carboxylic, dicarboxylic or sulfonic acid radical, or
are each, individually or together, an aromatic ring from the group consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, which may be unsubstituted or mono- to tetrasubstituted by A or Hal, or
are each, individually or together, a heterocyclic aromatic ring from the group consisting of pyridyl, pyrazyl and bipyridyl, which may be unsubstituted or mono- to trisubstituted by A or Hal, or
are each, individually or together, an aromatic hydroxy acid from the group consisting of aromatic hydroxycarboxylic acids and aromatic hydroxysulfonic acids, which may be unsubstituted or mono- to tetrasubstituted by A or Hal, and
Hal is F, Cl or Br
and
A is alkyl having 1 to 6 carbon atoms, which may be mono- to trihalogenated.
Likewise suitable are alkali metal alkoxides of the general formula
Li+ORxe2x88x92
in which R
is an aromatic or aliphatic carboxylic, dicarboxylic or sulfonic acid radical, or
is an aromatic ring from the group consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, which may be unsubstituted or mono- to tetrasubstituted by A or Hal, or
is a heterocyclic aromatic ring from the group consisting of pyridyl, pyrazyl and bipyridyl, which may be unsubstituted or mono- to trisubstituted by A or Hal, or
is an aromatic hydroxy acid from the group consisting of aromatic hydroxycarboxylic acids and aromatic hydroxysulfonic acids, which may be unsubstituted or mono- to tetrasubstituted by A or Hal,
and
Hal is F, Cl or Br
and
A is alkyl having 1 to 6 carbon atoms, which may be mono- to trihalogenated.
Lithium complex salts of the formula 
xe2x80x83where
xe2x80x83R1 and R2 are identical or different, are optionally bonded directly to one another via a single or double bond, and are each, individually or together, an aromatic ring from the group consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, which may be unsubstituted or mono- to hexasubstituted by alkyl (C1 to C6), alkoxy groups (C1 to C6) or halogen (F, Cl or Br),
or are each, individually or together, an aromatic heterocyclic ring from the group consisting of pyridyl, pyrazyl and pyrimidyl, which may be unsubstituted or mono- to tetrasubstituted by alkyl (C1 to C6), alkoxy groups (C1 to C6) or halogen (F, Cl or Br),
or are each, individually or together, an aromatic ring from the group consisting of hydroxybenzocarboxyl, hydroxynaphthalenecarboxyl, hydroxybenzosulfonyl and hydroxynaphthalenesulfonyl, which may be unsubstituted or mono- to tetrasubstituted by alkyl, (C1 to C6), alkoxy groups (C1 to C6) or halogen (F, Cl or Br),
R3-R6 may each, individually or in pairs and optionally bonded directly to one another via a single or double bond, have the following meanings:
1. alkyl (C1 to C6), alkoxy (C1 to C6) or halogen (F, Cl or Br)
2. an aromatic ring from the groups consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, which may be unsubstituted or mono- to hexasubstituted by alkyl (C1 to C6), alkoxy groups (C1 to C6) or halogen (F, Cl or Br),
pyridyl, pyrazyl and pyrimidyl, which may be unsubstituted or mono- to tetrasubstituted by alkyl (C1 to C6), alkoxy groups (C1 to C6) or halogen (F, Cl or Br),
which are prepared by the following process (DE 199 32 317):
a) chlorosulfonic acid is added to 3-, 4-, 5- or 6-substituted phenol in a suitable solvent,
b) the intermediate from a) is reacted with chlorotrimethylsilane, and the reaction mixture is filtered and subjected to fractional distillation,
c) the intermediate from b) is reacted with lithium tetramethoxyborate(1-) in a suitable solvent, and the end product is isolated therefrom,
may also be present in the electrolyte.
The electrolytes may likewise comprise compounds of the following formula (DE 199 41 566):
[([R1(CR2R3)k]1Ax)yKt]+ xe2x88x92N(CF3)2
where
Kt=N, P, As, Sb, S or Se
A=N, P, P(O), O, S, S(O), SO2, As, As(O), Sb or Sb(O)
R1, R2 and R3 
are identical or different
and are H, halogen, substituted and/or unsubstituted alkyl CnH2n+1, substituted and/or unsubstituted alkenyl having 1-18 carbon atoms and one or more double bonds, substituted and/or unsubstituted alkynyl having 1-18 carbon atoms and one or more triple bonds, substituted and/or unsubstituted cycloalkyl CmH2mxe2x88x921, mono- or polysubstituted and/or unsubstituted phenyl, or substituted and/or unsubstituted heteroaryl,
A can be included in R1, R2 and/or R3 in various positions,
Kt can be included in a cyclic or heterocyclic ring, the groups bonded to Kt may be identical or different,
where
n=1-18
m=3-7
k=0 or 1-6
l=1 or 2 in the case where x=1 and 1 in the case where x=0
x=0 or 1
y=1-4.
The process for the preparation of these compounds is characterized in that an alkali metal salt of the general formula
D+ xe2x88x92N(CF3)2
where D+ is selected from the group consisting of the alkali metals, is reacted, in a polar organic solvent, with a salt of the general formula
[([R1(CR2R3)k]1Ax)yKt]+ xe2x88x92E
where
Kt, A, R1, R2, R3, k, l, x and y are as defined above, and
xe2x88x92E is Fxe2x88x92, Clxe2x88x92, Brxe2x88x92, Ixe2x88x92, BF4xe2x88x92, ClO4xe2x88x92, AsF6xe2x88x92, SbF6xe2x88x92 or PF6xe2x88x92.
However, use can also be made of electrolytes comprising compounds of the general formula (DE 199 53 638)
Xxe2x80x94(CYZ)mxe2x80x94SO2N(CR1R2R3)2
where
X is H, F, Cl, CnF2n+1, CnF2nxe2x88x921 or (SO2)kN(CR1R2R3)2.
Y is H, F or Cl
Z is H, F or Cl
R1, R2 and R3 are H and/or alkyl, fluoroalkyl or cycloalkyl
m is 0-9 and, if X=H, mxe2x89xa00
n is 1-9
k is 0 if m=0 and k=1 if m=1-9,
prepared by reacting partially or perfluorinated alkylsulfonyl fluorides with dimethylamine in organic solvents, and complex salts of the general formula (DE 199 51 804)             M              X        +              ⁡          [      EZ      ]            x    /    y    y
xe2x80x83in which:
x and y are 1, 2, 3, 4, 5 or 6
Mx+ is a metal ion
E is a Lewis acid selected from the group consisting of
BR1R2R3, AlR1R2R3, PR1R2R3R4R5, AsR1R2R3R4R5 and VR1R2R3R4R5,
R1 to R5 are identical or different, are optionally bonded directly to one another via a single or double bond, and each, individually or together, are
a halogen (F, Cl or Br),
an alkyl or alkoxy radical (C1 to C8), which may be partially or fully substituted by F, Cl or Br,
an aromatic ring, optionally bonded via oxygen, from the group consisting of phenyl, naphthyl, anthracenyl and phenanthrenyl, which may be unsubstituted or mono- to hexasubstituted by alkyl (C1 to C8) or F, Cl or Br,
an aromatic heterocyclic ring, optionally bonded via oxygen, from the group consisting of pyridyl, pyrazyl and pyrimidyl, which may be unsubstituted or mono- to tetrasubstituted by alkyl (C1 to C8) or F, Cl or Br, and
Z is OR6, NR6R7, CR6R7R8, OSO2R6, N(SO2R6) (SO2R7) C(SO2R6)(SO2R7) (SO2R8) or OCOR6, where
R6 to R8 are identical or different, are optionally bonded directly to one another via a single or double bond and are each, individually or together,
hydrogen or as defined for R1 to R5,
prepared by reacting a corresponding boron or phosphorus Lewis acid/solvent adduct with a lithium or tetraalkylammonium imide, methanide or triflate.
Borate salts (DE 199 59 722) of the general formula 
in which:
M is a metal ion or tetraalkylammonium ion,
x and y are 1, 2, 3, 4, 5 or 6,
R1 to R4 are identical or different and are alkoxy or carboxyl radicals (C1-C8), which are optionally bonded directly to one another via a single or double bond, may also be present. These borate salts are prepared by reacting lithium tetraalkoxyborate or a 1:1 mixture of lithium alkoxide and a borate with a suitable hydroxyl or carboxyl compound in a ratio of 2:1 or 4:1 in an aprotic solvent.
The positive-electrode materials according to the invention can likewise be employed in systems with polymer-coated lithium mixed oxide particles for negative-electrode materials (DE 19946066). The process for the production of lithium mixed oxide particles coated with one or more polymers is characterized in that the particles are suspended in a solvent, and the coated particles are then filtered off, dried and, if desired, calcined. The positive-electrode materials according to the invention can also be employed in systems with negative electrodes consisting of lithium mixed oxide particles coated with one or more metal oxides (DE 19922522). The process for the production of lithium mixed oxide particles coated with one or more metal oxides is characterized in that the particles are suspended in an organic solvent, a solution of a hydrolysable metal compound and a hydrolysis solution are added to the suspension, and the coated particles are then filtered off, dried and, if desired, calcined.
A general example of the invention is explained in greater detail below.
The starting compounds employed are about 1-about 2 molar, preferably about 2 molar, tin tetrachloride solutions. The solution is introduced into water with cooling and vigorous stirring. The white precipitate formed in the case of the Sn system is dissolved by warming. After the mixture has been cooled to room temperature, the amount of urea corresponding to the system is added and dissolved completely. The addition of the urea and the dissolution behaviour are system-dependent.
Through addition of water, the dissolved concentration of the solution is set (see information above). The solution is cooled to temperatures from 0-about 10xc2x0 C., preferably about 5-about 7xc2x0 C. An about 3.5 molar hexamethylenetetramine solution is added in the preferred ratio about 1:1. The ratio also applies to the tin system. It is also possible to use about a 10% sub- or superstoichiometric amount of hexamethylenetetramine. The mixture is stirred until the sol is clear.
Benzine (petroleum ether) is mixed with about 0.5-about 1.5%, preferably about 0.7%, of commercially available emulsifiers, preferably with SPAN 80 emulsifier, manufactured by Sigma Aldrich Chemie GmbH of Eschenstr. 5, 82024 Taufkirchen (Germany). The solution is warmed to temperatures of about 30xc2x0 C.-about 70xc2x0 C., preferably to about 50xc2x0 C. The solution described above is added with constant stirring. An ammonia solution is added to the forming gel after about 3-about 20 minutes, preferably after about 10 minutes, and the pH is stabilized so that no peptization of the gel occurs. After the organic phase has been decanted, the gel is washed with a suitable organic solvent, preferably with petroleum ether or benzine having a boiling point of about 63-140xc2x0 C. In order to remove the emulsifier and organic impurities, detergents, preferably TRITON detergent, manufactured by Sigma Aldrich Chemie GmbH, Eschenstr. 5, 82024 Taufkirchen (Germany); are subsequently added to the solution. The solution is filtered with suction, and the gel is washed with water and acetone.
The gel is dried and, if desired, subjected to heat treatment. If an SnO system is desired, drying to a maximum of about 230xc2x0 C., preferably at about 75xc2x0 C.-about 110xc2x0 C., is sufficient. If an SnO2 system is desired, the drying is followed by heat treatment. The heat treatment is carried out at temperatures of about 230xc2x0 C.-about 500xc2x0 C., preferably about 55xc2x0 C.-about 350xc2x0 C., and optimally at about 350xc2x0 C. The heat treatment is carried out for about 10 minutes- about 5 hours, preferably about 90 minutes-about 3 hours, and optimally for about 2 hours.
The heat-treated material is aerated with a reducing gas in an aeratable furnace, for example a muffle furnace, a tubular furnace or a chamber furnace. The reduction gas mixture can be, for example, hydrogen and argon or nitrogen. The gas stream is set to about 5-about 15 litres/hour, preferably to about 10 litres/hour. The reduction gas mixture is fed to the system for a period of about 0.5-about 5 hours, preferably about 2.5-about 3.5 hours.
The temperature for the reduction process can be varied from about 230xc2x0 C.-about 600xc2x0 C., preferably about 300-about 500xc2x0 C., and optimally at about 500xc2x0 C.
Depending on the duration of exposure to the temperature and the amount of reducing gas, different concentrations of Sn in the SnO2 matrix are formed. For the electrochemical properties of the electrochemical cell, a concentration of Sn in the SnO2 matrix of about 20-about 70% by weight, preferably about 30-about 40%, and optimally about 38%, has become desirable for the positive-electrode material. In addition, different concentrations of Sn can be formed in a SnO matrix. Generally, a concentration of Sn in SnO matrix is about 10-about 40% by weight, preferably about 20-about 35% by weight, and optionally about 30% by weight.
The measured capacity of the positive electrode consisting of an SnO2/Sn system is still remarkably approximately 600 mAh/g after the 3rd cycle.
The initial capacity is significantly higher than in the case of the carbon positive electrode. With progressing cycling, the capacity of the carbon is achieved.
The reversibility, i.e. the effective charging and discharging of the cells, is about 90%.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
In the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees Celsius; and, unless otherwise indicated, all parts and percentages are by weight.
The entire disclosure of all applications, patents and publications, cited herein and corresponding German Application No. 10025762.3, filed May 25, 2000, is hereby incorporated by reference.